Radial block copolymers and adhesives based thereon with improved die-cutting performance

ABSTRACT

Improved adhesives are provided through the use of styrenic radial block copolymers, containing at lest 40 wt % diblock copolymers, the adhesives have improved adhesive properties and a reduced elastic behaviour under die-cutting conditions. Compared to conventional linear block copolymers of similar molecular weight, radial copolymers offer higher holding power and lower melt viscosity for the adhesive. They therefore contribute to an improved balance between processability and end-use properties.

FIELD OF THE INVENTION

The present invention is directed to radial block copolymer compositionsand pressure-sensitive adhesive compositions based thereon. Thepressure-sensitive adhesives are particularly useful in label and tapemanufacture.

BACKGROUND

Radial block copolymers are known and it is also known that during theirmanufacture up to 20 wt % of the diblock copolymers remain unreacted andare present as diblock copolymer material. These low diblock contentradial copolymers have been proposed as components in pressure-sensitiveadhesives, where they are used to make during label manufacture, alaminate of a face stock, pressure-sensitive adhesive layer, and arelease liner, such as silicone-coated paper, which is passed through anapparatus that converts the laminate into commercially useful labels andlabel stock. The converting operation processes involve printing,die-cutting, and matrix stripping to leave labels on a release liner,marginal hole punching, perforating, fan folding, guillotining and thelike. It is important that the cutting action breaks the face stock andadhesive layer, but does not indent the release liner. Producing aseries of labels on a backing sheet involves cutting around the labeland removing the material between two labels (the matrix) while leavingthe label itself attached to the backing sheet. It is important that thedie-cutting machine make a clean break at operating speeds. The adhesivewith the copolymer of low diblock content is formulated to have thedesired viscoelastic and adhesive properties so that it can be appliedto the release liner or the face-stock back, and will remain on thelabel after stripping and will have the required adhesion. But these areproperties that make the adhesive film difficult to cut or break. Theseproperties make die-cutting difficult and inconsistent, causing theadhesive lends to form adhesive strings and deposits on the cuttingblade. FIG. 1 illustrates a typical die-cutting process.

Die-cutting involves cutting the laminate through to the release linerface. Other procedures involve cutting completely through the labellaminate and include hole punching, perforating, and guillotining,particularly on flat sheets.

The cost of converting a laminate into a finished product, such as alabel, is a function of the various processing operations' rates. Linespeed depends on whether a printing step is involved. If there is noprinting as with, for example, computer labels, speeds can reach 300meters/minute. If label printing is involved, then speeds of 50-100meters/minute are typical. While the nature of all laminate layersimpact convertibility cost, the adhesive layer can limit convertibilityease. The adhesive layer's viscoelastic nature causes this limitation—inparticular its high elasticity prevents it from flowing away from thecut line during die-cutting and also promotes its transfer to cuttingblades during cutting. High adhesive elasticity also causes adhesivestringiness, which hinders matrix stripping as the unwanted facingmaterial is removed after die-cutting. High elasticity also promotesadhesive layer reconnection after the layer is severed.

Achieving good convertibility does not necessarily coincide withachieving excellent adhesive performance. Adhesives must be formulatedto fit needs, and important properties include peel adhesion, tack,shear, and viscosity at various temperatures and adhesion on varioussubstrates such as polymers, papers, glasses, and steels. Good,general-purpose adhesives may exhibit poor convertibility simply becausethe adhesive is difficult to cleanly sever. The adhesive may stick to adie or blade. As previously discussed in label manufacture, die-cuttingand matrix stripping operations occur at speeds from 5-300 meters perminute, typically 50-100 meters per minute, if printing is involved.Within a range of speeds, use of a particular adhesive may result inbreaking the matrix despite the fact that successful matrix strippingcan occur at speeds on either side of the breaking speed. One goal is toprovide adhesive systems where the adhesive has good die-cuttingperformance and where the matrix can be successfully stripped over theentire operating speed range.

Typical label adhesives are produced from acrylic polymer emulsions,which may be tackified by hydrocarbon or natural-resin tackifiers. Whilethese have good die-cutting performance, they require handling largevolumes of liquid and subsequent liquid removal. Accordingly, adhesivesapplied as hot melts would be preferred. At low temperature,acrylic-based adhesives perform poorer than hot-melt systems. Moreover,hot melts can be used at faster line application speeds in a broadertemperature range, have more aggressive tack, and can be used underhumid conditions. It is however important that the adhesive has desiredrheological properties both for processability such as coating and atend use temperature.

Hot-melt pressure-sensitive adhesive systems are well known and consistof tackified thermoplastic elastomers such as styrenic block copolymerstogether with tackifying resin(s) and generally some plasticizing oil,an antioxidant and optionally fillers. Styrenic block copolymerscontaining polystyrene and polybutadiene blocks and/or polyisopreneblocks are particularly useful. These materials are generally availableas pure triblocks, (sometimes referred to as SIS and SBS copolymers),and diblocks (sometimes referred to as SI and SB copolymers). Thematerials are also available as mixtures of diblock and triblockmaterials (sometimes referred to as SIS+SI and SIS+SB). Examples ofthese materials are the Vector materials marketed by Dexco and theKraton D materials marketed by Kraton Polymers. Radial block copolymershave also been proposed.

It is known to use diblock/triblock blends as the elastomeric componentin hot-melt pressure-sensitive adhesives. It is further known thatadhesive properties and viscosity can be controlled by varying thediblock-to-triblock ratio, varying the styrene content, varying thepolymer molecular weight, and varying the block molecular weights withinthe polymers. The melt viscosity can also be controlled by the additionof plasticizing oils and varying the molecular weight of the polymers.Examples of materials that have been used are Kraton D 1113, containing16% styrene and 56% diblock; Quintac 3433, marketed by Nippon Zeon,containing 55% diblock and 17% styrene; Vector 4114, containing 42%diblock and 17% styrene; and Vector 4113 containing 20% diblock and 17%styrene. Vector 4114 and Vector 4113 are Dexco products. While thesematerials have good adhesive properties when tackified and can be usedin hot melts for label production, they do not have optimum die-cuttingproperties. Furthermore, their balance of adhesive properties are notoptimum.

U.S. Pat. No. 5,663,228 concerns improving label adhesivedie-cuttability. But the proposed solution is different and morecomplicated than the present invention and requires the use of twoparticular block copolymer resins having certain glass-transitiontemperatures and the choice of a tackifying resin that, when mixed withthe two particular block copolymers, increases the difference betweenthe two block copolymers' glass transition temperatures. U.S. Pat. No.5,663,228 also does not appreciate the importance of the adhesive'selastomeric behavior under die-cutting conditions. Examples of styreniccopolymers that are used in the adhesive mixtures of U.S. Pat. No.5,663,228 are Finaprene 1205 available from AtoFina and Kraton 1107available from Kraton Polymers.

U.S. Pat. No. 5,412,032 concerns linear SIS triblock/diblock copolymersthat can be used in labels to improve die-cutting. This is accomplishedusing block copolymers with a styrene content from 18 to 24 wt %, apolystyrene block molecular weight from 25,000 to 35,000 an overallmolecular weight of above 280,000 up to 520,000 and a couplingefficiency of 20% to 40%. The coupling efficiency corresponds to thepercentage of triblock material in the overall block copolymer.

PCT Patent applications PCT/US01/20671 and PCT/US01/20609 describe theuse of certain diblock/triblock blends and the use of tetrablock andpentablock copolymers in label adhesives to improve die-cuttingperformance.

It is also known to use radial block copolymers in hot melt adhesives.For example, U.S. Pat. Nos. 5,194,500 and 5,750,607 relate tostyrene-isoprene three arms block copolymers and their use in adhesives.These three arms radial copolymers are available as Kraton 1124 fromKraton Polymers and Quintac 3450 and Quintac 3460C from Nippon Zeon.International Patent publications WO 92/20725 and WO 95/14727 areconcerned with radial block copolymers comprising polystyrene blocksegments and diene block segments, the diene block segment is preferablypredominately polyisoprene block containing a small amount of butadieneat the end of the diene block to ensure multi arms coupling. Thesepublications also disclose the use of these polymers in hot meltadhesive systems. WO 92/20725 is primarily concerned with the use ofsuch polymers in adhesives used in disposable articles. WO 95/14727 isconcerned with achieving optimum balance between high holding power andlow melt viscosity of the adhesives.

European Patent Application 0798358 A1 is concerned with hot meltadhesives, particularly hot melt adhesives for labeling which have areduced viscosity. The adhesives have a low diblock content and we havefound that this results in an adhesive that is too cohesive and has highelasticity which is detrimental for die cuttability as is shown inComparative Example 1 which is based on the radial polymer DPX-551mentioned in European Patent Application 0798358 A1 as a suitablepolymer for use in its adhesive formulations.

The radial block copolymers of WO 95/14727 are characterised by theformula:(pS−pI−pB)_(n)X  (1)wherein pS is polystyrene, pI is polyisoprene, pB is polybutadiene, X isa residue of a multifunctional coupling agent used in the production ofthe radial block copolymer, and n is a number greater than or equal to 3and representative of the number of branches appended to X. According toWO 95/14727 the number n is predominately 4. The molecular weight of thepS block of the radial block copolymer is between about 10,000 to about15,000 g/mole, preferably from about 12,000 to about 14,000 g/mole. ThepI−pB block preferably has a total average number molecular weight(polystyrene equivalent molecular weight) ranging from about 40,000 toabout 130,000 g/mole, preferably from about 50,000 to about 115,000g/mole. The overall number average molecular weight (polystyreneequivalent) of the radial block copolymer ranges from about 200,000 toabout 400,000 g/mole, preferably from about 225,000 to about 360,000g/mole, and the polystyrene block pS component is present in an amountof at least about 14 to about 24 parts, preferably from about 15 toabout 22 parts, per 100 parts by weight of the radial block copolymer.

The radial block copolymers of WO 95/14727 are thus constituted ofpolystyrene block segments and polydiene block segments in accordancewith formula (1). The copolymers may be random, tapered, block or acombination of these, provided that the polybutadiene segment acts asthe terminus segment of the polydiene block so that it may react withthe coupling agent. The other endblock of the polymer is polystyrene.

The pS segment is generally prepared by sequentially polymerizingstyrene. In accordance with formula (1), isoprene is employed to makethe pI segments, the (pS−pI) polymer chains being formed by sequentialpolymerization of isoprene with the pS. The pS−pI−pB−Li polymer chainsare then formed by the sequential polymerization of living pS−pI−Lipolymer chains with butadiene.

The radial or multiblock (pS−pI−pB)_(n)X copolymers are correspondinglymade by coupling the pS−pI−pB−Li living polymer chains with a multi- ortetra-functional coupling agent, such as SiCl₄. Thus, the styrene ispolymerized to form pS, the isoprene is then introduced to form pS−pI,the butadiene is then introduced to form pS−pI−pB, and the pS−pI−pBchains are then coupled with the tetrafunctional coupling agent to formthe (pS−pI−pB)_(n)X radial or multiblock polymer. The polymer isgenerally recovered as a solid such as a crumb, powder or pellet.

In the pI−pB segment of the (pS−pI−pB)_(n)X polymer, the polyisoprene ispresent in an amount sufficient to impart predominantly polyisoprenecharacteristics, not butadiene or polybutadiene characteristics, to thepolymer. Thus, in the pI−pB segments of the polymer, the weight amountof polyisoprene will exceed 50% of the total weight of diene in thepolymer, i.e., pI/(pI+pB)>50 wt %. Conversely, the weight amount ofbutadiene or polybutadiene will be less than 50% of the total weight ofdiene in the polymer, i.e., pB/(pI+pB)<50 wt %. Preferably, thepolybutadiene portion of the diene segment is less than 10%, mostpreferably less than 5%, based on the total weight of the (pI+pB), ordiene component of the polymer.

The small amount of butadiene at the end of the diene midblock is usefulin that it enhances the coupling reaction in formation of the radialpolymer, and results in a radial polymer with a higher number ofbranches.

The radial polymers of WO 95/14727 are thus synthesized by firstcontacting styrene with an initiator, suitably, for example, asec-butyllithium initiator, in the presence of an inert diluent, forexample, cyclohexane. A living polymer is then formed, as represented,for example, by the simplified structure pS−Li. The living polystyrenepolymer pS−Li is next reacted with an isoprene monomer; the resultingproduct being represented by the simplified structure pS−pI−Li. Theliving polymer pS−pI−Li is then reacted with a small amount of butadienemonomer to produce a living polymer with the structure pS−pI−pB−Li, pBrepresents butadiene or polybutadiene. Coupling of the pS−pI−pB−Li withthe coupling agent produces a branched block copolymer with thestructure (pS−pI−pB)_(n)X. The radial polymer that is produced, usingSiCl₄ as a coupling agent, will render (pS−pI−pB)_(n)X polymer where nis predominantly 4, i.e. more than 50 wt % of the radial copolymer isfour arms. The butadiene need be added only in an amount necessary toassure that the ends of all of the pI segments of the polymer chains areprovided with at least one molecule of butadiene, though as suggestedthe butadiene can be added in larger or smaller amounts.

Coupling agents which may be used to produce the radial polymers ofW095/14727 include those possessing four sites reactive towardcarbon-lithium bonds. Suitable coupling agents are those compositions ofthe formula X(L)_(n) where X represents the coupling moiety residue, andL is suitable leaving group. Exemplary of coupling agents of this typeare silicon halides, for example, SiCl₄, or a silane compound where oneor more of the halides is substituted by an alkoxy group, for example,tetramethoxysilane or tetraethoxysilane compounds, epoxy compounds, forexample, epoxidised linseed oil, epoxidised soybean oil; acrylate multiesters, for example, pentaerythritol tetraacrylate; epoxy silanes,divinyl compounds, for example, divinyl benzene, and the like.

In addition to polystyrene, other alkenyl aromatic hydrocarbon monomers,such as alkyl-substituted styrenes, alkoxy-substituted styrenes, 2-vinylpyridine, 4-vinyl pyridine, vinyl naphthalene, alkyl-substituted vinylnaphthalenes and the like. For simplicity herein, the terms styrene,styrenic, polystyrene content-and polystyrene equivalent molecularweight as used in this application are intended to include these otheralkenyl aromatic hydrocarbons.

The isoprene polymerization technique is preferably such that thestereochemistry of the polymerisable monomer is adjusted so thatpredominantly cis-1,4-polyisoprene having a glass transition temperatureof less than −50° C. as measured by differential scanning calorimetry ata 10° C. per minute temperature scan rate is produced.

The radial block copolymers are preferably produced by solution anionictechniques, although they could be prepared using bulk, solution oremulsion techniques. Such techniques entail contacting the monomers tobe polymerized simultaneously or sequentially with an organoalkali metalcompound in a suitable solvent at a temperature within the range fromabout −100° C. to about 150° C., preferably at a temperature within therange from about 0° C. to about 100° C. Particularly effective anionicpolymerization initiators are organolithium compounds having the generalformula:RLi_(n)wherein:

R is an aliphatic, cycloaliphatic, aromatic or alkyl-substitutedaromatic hydrocarbon radical having from 1 to about 20 carbon atoms; andn is an integer of 1 to 3.

In general, any of the solvents known to be useful in the preparation ofsuch polymers may be used. Suitable solvents include straight- andbranched chain hydrocarbons such as pentane, hexane, heptane, octane andthe like, as well as alkyl-substituted derivatives thereof,cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane,cycloheptane and the like, as well as alkyl-substituted derivativesthereof, aromatic and alkyl-substituted aromatic hydrocarbons such asbenzene, toluene, xylene and the like; hydrogenated aromatichydrocarbons, such as tetralin, decalin and the like. Linear and cyclicethers such as dimethyl ether, methyl ethyl ether, anisole,tetrahydrofuran and the like may be used in small amounts.

During the coupling reaction involved in producing radial blockcopolymers not all the polymer will be coupled. The coupling efficiencyof radial block copolymers is defined as the mass of coupled polymerdivided by the mass of coupled polymer plus the mass of uncoupledpolymer. The coupling efficiency herein refers to that of the originalpolymer not including any degradation fragments formed duringprocessing. Thus, when producing the (pS−pI−pB)_(n)X branched polymers,the coupling efficiency is shown as a percentage by the followingrelationship:$\frac{{mass}\quad{of}\quad{coupled}\quad{polymer}}{{mass}\quad{of}\quad\left( {{uncoupled} + {coupled}} \right){polymer}} \times 100\quad(\%)$

Coupling efficiency can be measured by an analytical method such as gelpermeation chromatography.

Coupling efficiency can be controlled by a number of methods. One methodto reduce coupling efficiency is to add less than the stoichiometricamount of coupling agent required for complete coupling of the polymers.Another means of reducing coupling efficiency is by the prematureaddition of a terminator compound. These terminators, such as water oralcohol, react very quickly and can easily be employed to cut shortcomplete coupling of the polymers. In addition, by performing thecoupling reaction at elevated temperatures, such as above about 90° C.,thermal termination of many of the living polymer groups (pS−pI−Li)occurs prior to coupling. The typical coupling conditions include atemperature of between about 65° C. to about 75° C. and sufficientpressure to maintain the reactants in a liquid phase.

Following the coupling reaction or when the desired coupling efficiencyhas been obtained, any remaining uncoupled product is terminated such asby the addition of terminators, for example, water, alcohol or otherreagents, for the purpose of removing the lithium radical forming thenucleus for the condensed polymer product. The product is then recoveredsuch as by coagulation utilizing hot water or steam or both, oralternatively by the use of a devolatilizing extruder.

Radial four arms block copolymers and their use in hot melt adhesivesare also described in European Patent Application 1103577 A1 and U.S.Pat. No. 5,292,819.

The three and four arms products of these patents and the commerciallyavailable materials suffer from the disadvantages that they do not haveoptimum rheological properties for use in permanent label adhesives. Wehave found that they have a coupling efficiency greater than 60%,generally greater than 70% and accordingly contain less than 40 wt % ofdiblock copolymer. These polymers tend to have too high a tensilestrength and are harder and too cohesive to be useful in adhesiveformulations and in other applications such as sound deadening, shockabsorption and polymer modification.

We have now developed radial block copolymer compositions which overcomethese problems.

We have found that, unlike the known products, if the diblock copolymercontent of a mixture of a radial styrenic block copolymer and a styrenicdiblock copolymer is above 40 wt % of the total block copolymer content,an adhesive system having improved rheological and improved die-cuttingperformance with desirable adhesive properties may be obtained. Some orall of the diblock may be produced during the manufacture of the radialcopolymer.

Surprisingly, we found that die-cutting takes place at relatively lowdeformation rates and involves pushing the adhesive to the side of theline of cut rather than involving a sharp cutting action. In successfuldie-cutting, the adhesive must creep when subjected to cutting knifeaction, flow away from the cut point, and not reform over the cut line.

The creep of the adhesive may be illustrated by assuming typicalconditions of die-cutting operations, i.e. a machine line speed of 100m/min, a rotating cylinder of 10 cm diameter, and face paper andadhesive layers with a thickness of 80 and 20 microns respectively.Since the diameter of the rotating cylinder is much larger (by a factor100) than the overall thickness to indent, the effective vertical motionis only 10 cm/s when the knife starts to indent the face paper, and only2 cm/s when the adhesive itself is indented.

The second aspect has been discovered with the help of finite-elementsimulations of the die-cutting process performed with Abacus Software.These showed that the adhesive is pushed away by the much stiffer facepaper, well before the cutting knife starts to indent the adhesivelayer. In other words, the adhesive layer flows under the pressureimparted by the cutting knife on the face stock, which covers theadhesive layer. In most instances, no direct contact between the knifeand the adhesive layer occurs.

The simulation of the die-cutting is shown in FIG. 2, in which 1 is therelease paper, 2 the adhesive layer, 3 is the frontal paper and 4 is thedie-cutting blade which is moving in an anticlockwise direction to makethe cut. The simulation shows how as the knife crushes and breaksthrough the paper, the adhesive layer is pushed away under the paperfrom the line of cut, but that the knife itself does not cut through theadhesive layer. Accordingly the more readily the adhesives flows and theless elastic it is, the easier and cleaner the cut will be.

Altogether, both the surprisingly low deformations rates involved in thedie-cutting process, as well as the need for the adhesive layer toundergo permanent flow during die-cutting operations explains whywater-based acrylic adhesives behave better than their triblock (forexample, SBS or SIS) counterparts. These two systems provide goodexamples of good and bad die-cutting behavior respectively.

Viscoelastic behavior of hot-melt adhesives at a given temperature isconveniently captured by the two dynamic moduli known as G′ and G″, theloss modulus G″ giving an indication of the viscous behavior, and thestorage modulus G′ giving an indication of the elastic behavior. Theratio of G″ and G′ is known as the loss factor Tangent delta (Tanδ).

The finding that the cutting mechanism pushes the adhesive away from theline of cut rather than performing a sharp cut, leads to the conclusionthat the adhesive should be less elastic to enable it to permanentlyflow away from the line of cut at the cutting temperature, normally roomtemperature. Emphasis should be put on the low frequency behaviorbecause of the surprisingly small values for the vertical velocity ofthe knife during die-cutting operations.

Dynamic mechanical analysis of acrylics systems shows indeed that thestorage modulus G′ continuously decreases with frequency, with noindication of a constant plateau at low frequencies. At the same time,there is a relatively high loss modulus G″ at low frequency, essentiallyoverlaying with G′. This amplifies the tendency of the adhesive toundergo permanent deformation and flow under stress, as shown in FIG. 3.On the other hand, similar analysis of previous pure triblock copolymerbased adhesives shows a constant and relatively high plateau modulus G′(>10,000 Pa) in the low frequency region, much higher than the lossmodulus G″, reflecting the tendency for the adhesive to recover fromdeformation, which is undesirable for die-cutting.

We have found that there is also a marginal difference at highfrequency, between the behavior of acrylics and the systems of thepresent invention (glass transition region and glassy domain),especially in the glass transition location on the frequency axis. Therheological behaviour at these frequencies can be modified by changingthe tackifier package, which is known to minimally influence die-cuttingbehavior.

Accordingly, we have found that, to have good die-cutting performance,an adhesive based on radial copolymers should fulfill the followingcriteria:

G′ at room temperature should decrease monotonically with frequency, atfrequencies below the glass transition region (typically<10 rad/s), downto a constant storage modulus plateau at the lowest frequencies. Theelastic modulus plateau should be lower than 8,000 Pa, preferably lowerthan 6,000 Pa, more preferably lower than 5,000 Pa, most preferablylower than 4,000 Pa, when measured at 20° C.

G′ should intersect a value of 10,000 Pa at a frequency that ispreferably higher than 0.001 rad/s; preferably higher than 0.01 rad/smore preferably higher than 0.05 rad/s; most preferably higher than 0.1rad/s, when measured at 20° C.

The loss factor Tanδ defined as the ratio G″/G′ preferably comprisesbetween 0.2 and 1.3, more preferably between 0.2 and 1.0, morepreferably 0.3 to 1.0, more preferably 0.4 to 1.0, most preferably 0.6to 1.0, at the frequency at which the storage modulus intersects a valueof 10000 Pa, when measured at 20° C.

We have found that, in addition to the improved adhesion performances,desirable die-cuttability properties may be achieved using an adhesivesystem containing a styrenic block copolymer which contains a radialblock copolymer and at least 40 wt % of a diblock styrenic copolymer.

SUMMARY

The present invention therefore provides a radial block copolymercomposition and a pressure-sensitive adhesive composition based thereon.The pressure-sensitive adhesive was found to exhibit excellent adhesiveproperties and convertibility. The adhesive provides the ability toachieve clean rupture of the adhesive layer in processing operationsinvolving cutting through a face stock to the release liner of thelaminate. At the same time the adhesive provides excellent adhesiveproperties at both ambient and reduced temperatures, in particular theadhesive has high shear performance thus increasing flexibility informulation. The adhesive is particularly suitable for use in labels onboth paper and synthetic substrates. The adhesive also has low meltviscosity and may be applied as a hot melt, at low temperature.

Accordingly the present invention provides a mixture of radial styrenicblock copolymer and styrenic diblock copolymer comprising from 60 wt %to 10 wt % of radial styrenic block copolymer and from 40 wt % to 90 wt% of styrenic diblock copolymer.

In a preferred mixture the radial styrenic block copolymer consists ofI) a polystyrene block segment and ii) a polyisoprene block segmenthaving an end which comprises butadiene, wherein the block copolymer ischaracterised by the formula:(pS−pI−pB)_(n)XpS being polystyrene, pI being polyisoprene, pB being polybutadiene, Xbeing the residue of a multifunctional coupling agent used in theproduction of the radial block copolymer and n being a number greaterthan or equal to 3 and representing the average number of branchesappended to X, and further wherein the pS component is present in anamount of at least 10 parts to about 35 parts per 100 parts by weight ofthe radial block copolymer; and the weight amount of polybutadiene inthe pI−pB segment being less than 50 wt %. We prefer that n ispredominantly 4.

We further prefer that the weight amount of polybutadiene in the pI−pBsegment is less than 10 wt %.

The present invention further provides an adhesive system comprising atackifier and a mixture of a radial styrenic block copolymer and astyrenic diblock copolymer comprising from 60 wt % to 10 wt % of theradial styrenic block copolymer and from 40 wt % to 90 wt % of thestyrenic diblock copolymer.

The invention further provides the use in an adhesive of a mixture of aradial styrenic block copolymer and a styrenic diblock copolymercomprising from 60 wt % to 10 wt % of the radial styrenic blockcopolymer and from 40 wt % to 90 wt % of the styrenic diblock copolymer.

In a preferred embodiment the radial block copolymer is predominantly afour arms radial block copolymer, is made by the process described in WO95/14727 and has the properties described above in relation to thepolymers of WO 95/14727. The process used to manufacture the four armscopolymers, as described above, generally results in the production of asmall amount, typically no more than 10 wt %, of a three arms radialcopolymer.

In another preferred embodiment the radial block copolymer has amolecular weight (Mw) above 200,000 g/mole preferably above 240,000g/mole. It is further preferred that the molecular weight be no greaterthan 500,000 g/mole, more preferably no greater than 400,000 g/mole. Itis yet further preferred that the radial block copolymer be a four armscopolymer of molecular weight from 240,000 g/mole to 500,000 g/mole,preferably to 400,000 g/mole, more preferably to 375,000 g/mole.

The use of the adhesive systems of the present invention has been foundto enable improved die-cuttability in the production of labels. Theinvention therefore further provides the use of a mixture of a radialstyrenic block copolymer and a styrenic diblock copolymer comprising 60wt % to 10 wt % of the radial styrenic block copolymer and 40 wt % to 90wt % of the styrenic diblock copolymer in label adhesives. Furthermore,we have found that the use of these copolymer mixtures provide adhesiveswith lower melt viscosity and higher shear resistance.

The invention further provides an adhesive composition providingimproved die-cuttability performance when used as a hot melt labeladhesive of a mixture of a tackifier and a mixture of a radial styrenicblock copolymer and a styrenic diblock copolymer comprising 60 wt % to10 wt % of the radial styrenic copolymer rubber and containing 40 wt %to 90 wt % of the styrenic diblock copolymer.

DETAILED DESCRIPTION

The radial copolymers of the present invention are preferably composedof polystyrenic block segments, polydiene block segments, suitablypolyisoprene block, or a predominantly polyisoprene block containing arelatively small amount of polybutadiene. Four arms radial copolymersare preferred.

The radial styrenic copolymers may be prepared by any suitablepolymerisation technique such as living anionic polymerization. Suchpolymer synthesis is described in U.S. Pat. Nos. 5,292,819 and5,399,627. Radial copolymers being the result of a coupling mechanismbetween two “living” prepolymers, do contain varying amount of diblocks.As a result such diblock molecular weight is identical to the molecularweight of each radial arm.

The block copolymer compositions of the present invention may beproduced by controlling the coupling efficiency of the coupling reactionso that at least 40 wt % of the diblock material remains uncoupled, thatis to say a coupling efficiency of less than 60%. This may be achievedby using the manufacturing techniques described in WO 95/14727 as forexample by reducing the amount of coupling agent that is used.Alternatively the block copolymer compositions may be obtained byblending additional diblock material into the radial block copolymer(which may already contain some unreacted diblock material) to obtain amixture containing the desired level of diblock material.

In the adhesives of the present invention the radial copolymer diblockcopolymer mixture is preferably used as the only copolymer in theadhesive system. Alternatively however they may be mixed with otherpolymers, particularly other styrenic block copolymers such as diblockand triblock copolymers or mixtures thereof.

The block copolymers of the invention are preferably of styrene andisoprene. In order to get good die-cutting performance, the vinylaromatic hydrocarbon content (generally styrene) of both the radialblock copolymer and the diblock copolymer should be at least 10,preferably at least 11, more preferably at least 12, more preferably atleast 13, more preferably at least 14, and more preferably at least 15%by weight. Similarly, the vinyl aromatic hydrocarbon content should beat or below 35, preferably at or below 34, preferably at or below 33,preferably at or below 32, preferably at or below 31, preferably at orbelow 30, preferably at or below 29, preferably at or below 28,preferably at or below 27, preferably at or below 26, preferably at orbelow 25, preferably at or below 24, preferably at or below 23, morepreferably at or below 22, preferably at or below 21, preferably at orbelow 20, most preferably at or below 19% by weight. Preferred rangesfor the vinyl aromatic hydrocarbon content may combine any upper and anylower limit described herein. Using polymers with this vinyl aromaticcontent results in a good combination of rheological, die-cutting andadhesive performance. Lower levels of vinyl aromatics results in weakpolymers, which impart poor shear properties, and higher levels givestiff adhesives, which are not sufficiently pressure sensitive.

Accordingly, the invention provides rubbers having the combination ofstructure and rheology that, inter alia, achieves a combination of gooddie-cutting and adhesive properties in systems which use pressuresensitive adhesives. The adhesives are preferably applied as hot melts.The preferred rubbers of the present invention have the followingproperties:

-   -   i) an overall minimum styrene content greater than 10,        preferably 12, most preferably 15 wt %;    -   ii) an overall maximum styrene content of 35, preferably 27,        more preferably 22 wt %; and    -   iii) a maximum “pure” radial copolymer content of at most 60 wt        %, preferably at most 55%, more preferably at most 50%, more        preferably at most 45%, more preferably at most 40%, more        preferably at most 35%, most preferably at most 30% based on the        total amount of block copolymer present,    -   iv) a minimum diblock copolymer content of at least 40 wt %,        preferably at least 45 wt %, preferably at least 50 wt %,        preferably at least 55 wt %, more preferably at least 60 wt %,        most preferably at least 70 wt % based on the total amount of        block copolymer present.

The radial copolymers of the present invention are preferably styrenicfour arms.

Where the rubber contains block polymers in addition to those producedduring the manufacture of the radial block copolymers, these arepreferably styrene/isoprene block polymers, and it is preferred that themolecular weight of any added triblock material, particularly a SIStriblock material, is at least 50,000 g/mole, more preferably at least100,000 g/mole, and at most 300,000 g/mole, particularly preferred is150,000 to 200,000 g/mole. It is preferred that the molecular weight ofany added diblock material, be at least 50,000 g/mole preferably atleast 60,000 g/mole, more preferably 70,000 g/mole, most preferably atleast 80,000 g/mole and at most 150,000 g/mole, preferably 140,000g/mole, most preferably 110,000 g/mole. Where the styrene diblockmaterial is a styrene-butadiene material, it is preferred that it has amolecular weight from 50,000 to 150,000 g/mole, preferably 65,000 to130,000 g/mole, such as 65,000 to 110,000, most preferably 70,000 to90,000 g/mole. In every embodiment the total diblock content must exceed40 wt %. Preferred ranges for the molecular weights in this paragraphmay combine any upper and any lower limited set out above.

For purposes of this specification, molecular weight means peakmolecular weight as measured by Gel Permeation Chromatography (sometimesknown as size exclusion chromatography) on a polystyrene calibrationbasis. Commercially available polystyrene standards were used forcalibration and the molecular weights of copolymers were correctedaccording to Runyon et al, J. Applied Polymer Science, Vol.13 Page 359(1969) and Tung, L H J. Applied Polymer Science, Vol. 24 Page 953(1979).

In the case of the preferred mixture of four arms radial copolymers anddiblock copolymers, the molecular weight of the pure radial copolymerswere calculated as 4 times the measured molecular weight of the diblockmolecular weight i.e. calculated as four times the molecular weight ofthe diblock copolymer obtained during the polymerization reaction. Themolecular weights of the radial copolymers quoted in this applicationtherefore refers to the molecular weight of the pure radial copolymer.

A Hewlett-Packard Model 1090 chromatograph with a 1047A refractive indexdetector was used. The chromatograph was equipped with four 300 mm×7.5mm Polymer Laboratories SEC columns packed with five micron particles.These consisted of two columns with 10⁵ angstrom pore size, one columnwith 10⁴ angstrom pore size, and one with mixed pore sizes. The carriersolvent was HPLC grade tetrahydrofuran (THF) with a flow of 1 ml/min.Column and detector temperatures were 40° C., and run time was 45minutes.

Tackifier additives for use in the adhesives of this invention arechosen according to the nature of the particular rubber that is used.Most tackifiers may be used. Preferred tackifiers are resins fromaliphatic petroleum derivative streams containing 5-or-6-carbon-atomdienes and mono-olefins. The tackifiers range from materials that arenormally liquid at room temperature to those that are normally solid atroom temperature. The resins typically contain 40 wt % or more ofpolymerized dienes. The dienes are typically piperylene and/or isoprene.Useful tackifiers include Escorez 1310 LC and Escorez 2520 manufacturedby ExxonMobil Chemical, Piccotac 95 manufactured by Eastman Chemical,and the Wingtack resin family manufactured by Goodyear (with thenumerical designation being the softening point) such as Wingtack 95,which is a solid resin having a softening point of about 95° C., andWingtack 10, which is a liquid resin having a softening point of about10° C.

Other suitable tackifiers include resins such as aliphatic/aromaticresins, which may or may not be hydrogenated such as the products ECR373 having a softening point of about 90° C., or Escorez 2520 having asoftening point of about 20° C. manufactured by ExxonMobil Chemical.Hydrogenated polycyclic resins (typically dicyclopentadiene resins suchas Escorez 5300, 5320, 5340 and 5380 manufactured by ExxonMobilChemical) and the like may also be used. Hydrogenated polycyclicaromatic modified resins, such as Escorez 5690, 5600 and 5620,manufactured by ExxonMobil Chemical, may also be used. Hydrogenatedaromatic resins wherein a very substantial portion, if not all, of thebenzene rings are converted to cyclohexane rings (for example, theRegalrez family of resins manufactured by Eastman Chemical such asRegalrez 1018, 1033, 1065, 1078 and 1126 and Regalite R-100, and theArkon family of resins from Arakawa Chemical such as Arkon P-85, P-100,P-115 and P-125) may also be used.

Rosin, rosin esters, polyterpenes, and other tackifiers, which arecompatible with the polyisoprene and polybutadiene phases and to somedegree with the polystyrene end blocks, can also be added. All suchtackifiers may be used in hydrogenated or unhydrogenated form. Otheradditives include plasticizing oils such as Shellflex 371, manufacturedby Shell, Kaydol mineral oil, manufactured by Witco and Flexon 876manufactured by ExxonMobil, which are soluble in both the polyisopreneand polybutadiene phases combine any upper and any lower limit.Typically the adhesives may contain from 5 to 20 wt %, preferably from 5to 15 wt %, more preferably from 10 to 15 wt % of the plasticizing oil.Preferred ranges for the amount of plasticizing oil in this paragraphare set out above. Preferred ranges for the quantities set out in thisparagraph may combine any upper and any lower limits set out above.

The tackifier may be present from 50% by weight, preferably from 55%,more preferably from 60%, based on the total weight of tackifier andcopolymers. It may be present at up to 80% by weight, preferably up to75%, more preferably up to 70% by weight. Conversely, the blockcopolymers are present from 20%, preferably from 25%, more preferablyfrom 30%, by weight based on the weight of the tackifier and thecopolymers and up to 50%, preferably up to 45%, by weight based on thecombined weight of the tackifier system and the copolymers. The resinadditives are preferably a mixture of a normally solid tackifier such asEscorez 1310 LC and a normally liquid tackifier such as Wingtack 10 orEscorez 2520. Preferred ranges for the quantities set out in thisparagraph may combine any upper and any lower limits set out above.

Petroleum resins are well known and are generally produced byFriedel-Crafts or thermal polymerization of various feeds, which may bepure monomer feeds or refinery streams containing mixtures of variousunsaturated materials. Generally speaking, the purer the feed the easierto polymerize. For example, pure styrene, pure α-methyl styrene andmixtures thereof are easier to polymerize than a C₈/C₉ refinery stream.Similarly, pure or concentrated piperylene is easier to polymerize thanC₄ to C₆ refinery streams. But these pure monomers are more expensive toproduce than the refinery streams that are often biproducts of largevolume refining.

Aliphatic hydrocarbon resins can be prepared by cationic polymerizationof a cracked petroleum feed containing C₄, C₅, and C₆ paraffins,olefins, and diolefins also referred to as “C₅ monomers”. These monomerstreams are comprised of cationically polymerisable monomers such asbutadiene, 1,3-pentadiene (piperylene) along with cyclopentene, pentene,2-methyl-2-butene, 2-methyl-2-pentene, isoprene, cyclopentadiene, anddicyclopentadiene. The refining streams are purified usually by bothfractionation and impurity removal to obtain these feeds.

Polymerisations are catalyzed using Friedel-Crafts catalysts such asunsupported Lewis acids (for example, boron trifluoride (BF₃), complexesof boron trifluoride, aluminum trichloride (AlCl₃), or alkyl-aluminumhalides, particularly chloride). In addition to the reactive components,non-polymerisable components in the feed include saturated hydrocarbons,which can be co-distilled with the unsaturated components such aspentane, cyclopentane, or 2-methylpentane. This monomer feed can beco-polymerized with other C₄ or C₅ olefins or dimers. The feed should bepurified (typically by fractionation) to remove unsaturated materialsthat adversely affect the polymerization reaction or cause undesirablecolor of the final resin (for example, isoprene). Generally, C₅aliphatic hydrocarbon resins are synthesized using a piperyleneconcentrate stream that is fractionation-enriched to increase thepiperylene content and to reduce the difficult-to-polymerize, olefin anddiolefin content.

Typically, the feedstream includes at least 20 wt %, preferably 30 wt %,more preferably 50 wt %, monomer and up to 80 wt %, preferably 70 wt %,more preferably 30 wt %, solvent. The solvent may be an aromaticsolvent, such as toluene, xylenes, and aromatic petroleum solvents, ortheir mixtures. The solvent may include an aliphatic solvent. Mixturesof aromatic and aliphatic solvents may also be used. The solvent mayalso be recycled. The solvent may be a non-polymerisable feed component.

The feedstream may include at least C₄ to C₆ monomers, in whichcyclopentadiene and methylcyclopentadiene components may be removed fromthe feedstream by heating at a temperature between 100° C. and 160° C.and fractionally distilling. The monomers may include at least one ofisobutylene, butadiene, 2-methyl-2-butene, 1-pentene,2-methyl-1-pentene, 2-methyl-2-pentene, 2-pentene, cyclopentene,isoprene, cyclohexene, 1,3-pentadiene, 1,4-pentadiene, isoprene,1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, and dicyclopentadiene.

In accordance with another aspect, the feedstream can include at least30 wt %, preferably 50 wt %, of C₅ monomers, as described above and atleast 5 wt %, preferably 15 wt % of a co-feed including at least one ofpure monomer, C₉ monomers, and terpenes. Likewise, the feedstream caninclude up to 95 wt %, preferably 85 wt % of C₅ monomers, as describedabove and 70 wt %, preferably 50 wt %, of a co-feed including at leastone of pure monomer, C₉ monomers, and terpenes.

The feed may also contain an aromatic olefin. Preferred aromatic olefinsare those such as styrene, indene, and their derivatives. Particularlypreferred aromatic olefins include styrene, α-methylstyrene,β-methylstyrene, indene, substituted indenes, such as methylindenes, andvinyl toluenes. The aromatic olefins are typically present at levels ofat least 1 wt %, and at up to 50 wt %, more preferably 30 wt %, evenmore preferably 10 wt %.

Polymerisations may be continuous or batch processes. A batch processreaction time is usually at least 30 minutes, preferably 60 minutes, andno greater than 8 hours, preferably 4 hours at a reaction temperature.Polymerisation temperatures range from −50° C. to 150° C., preferably−20° C. to 100° C. Temperature significantly affects resin properties.Higher-molecular-weight and high-softening-point resins are prepared atlower reaction temperatures. Polymerisation may be stopped by removingthe catalyst from the hydrocarbon resin, for example, by filtration. Thehydrocarbon resin may be removed from a fixed bed reactor, whichincludes the catalyst. The hydrocarbon resin may be stripped to removeunreacted monomers, solvents, and low-molecular-weight oligomers. Theunreacted monomers, solvents, and low-molecular-weight oligomers may berecycled.

The monomer feed can be co-polymerized with C₄ or C₅ olefin or dimers aschain transfer agents. Up to 40 wt % preferably up to 20 wt % of chaintransfer agents may be added to obtain resins with lower molecularweight and narrower molecular weight distributions than can be preparedusing the monomer feed alone. Chain transfer agents terminate polymerchain growth such that polymer initiation sites regenerate. Componentsthat behave as chain transfer agents in these reactions include but arenot limited to isobutylene, 2-methyl-1-butene, 2-methyl-2-butene, ordimers or oligomers of these species. The chain transfer agent can beadded to the reaction in pure form or diluted in a solvent.

Preferred solvents are aromatic solvents—typically toluene, xylenes, orlight aromatic petroleum solvents. These solvents can be used fresh orrecycled from the process. The solvents generally contain less than 200ppm water, preferably less than 100 ppm water, and most preferably lessthan 50 ppm water.

Typically, the resulting resin has a number average molecular weight(Mn) of at least 400, a weight average molecular weight (Mw) of at least500, a Z average molecular weight (Mz) of at least 700, and apolydispersity (PD) as measured by Mw/Mn of at least 1.5 where Mn, Mw,and Mz are determined by Gel permeation chromatography. Similarly, theresin has a number average molecular weight (Mn) up to 2,000, a weightaverage molecular weight (Mw) of up to 3500, a Z average molecularweight (Mz) of up to 15,000 and a polydispersity (PD) as measured byMw/Mn up to 4.

Where hydrogenated resins are used, the hydrogenation may be carried outvia molten resin or resin solution-based processes by either batch wiseor, more commonly, continuous processes. Supported monometallic andbimetallic catalysts based on group -6, -8, -9, -10 or -11 elements aretypically used for hydrocarbon resin hydrogenation. Catalysts such assupported nickel (for example, nickel on alumina, nickel on charcoal,nickel on silica, nickel on kieselguhr, etc), supported palladium (forexample, palladium on silica, palladium on charcoal, palladium onmagnesium oxide, etc) and supported copper and/or zinc (for example,copper chromite on copper and/or manganese oxide, copper and zinc onalumina, etc) are good hydrogenation catalysts. The support materialtypically consists of porous inorganic refractory oxides such as silica,magnesia, silica-magnesia, zirconia, silica-zirconia, titania,silica-titania, alumina, silica-alumina, alumina-silicate, etc, withsupports containing y-alumina being highly preferred. Preferably, thesupports are essentially free of crystalline molecular sieve materials.Mixtures of the foregoing oxides are also contemplated, especiallyhomogeneous mixtures. Among the useful support materials in the presentinvention are the supports disclosed in the U.S. Pat. Nos. 4,686,030,4,846,961, 4,500,424, and 4,849,093. Preferred supports include alumina,silica, carbon, MgO, TiO₂, ZrO₂, FeO₃ or their mixtures.

Any of the known processes for catalytically hydrogenating hydrocarbonresins can be used; particularly the processes of U.S. Pat. Nos.5,171,793, 4,629,766, 5,502,104 and 4,328,090 and WO 95/12623. Generichydrogenation conditions include reaction temperatures of 100° C. -350°C. and hydrogen pressures of 5 atmospheres (506 kPa)-300 atmospheres(30390 kPa), for example, 10 to 275 atm (1013 kPa to 27579 kPa). Apreferred hydrogenation temperature is in the range 180° C. to 320° C.and a preferred pressure is in the range 15195 kPa to 20260 kPahydrogen. The hydrogen-to-feed volume ratio to the reactor understandard conditions (25° C., 1 atm (101 kPa) pressure) typically canrange from 20-200. For water-white resins 100-200 is preferred.

Another suitable process for resin hydrogenation is described in EP0082726. EP 0082726 describes hydrogenation of a catalytic or thermalpetroleum resin using nickel-tungsten catalyst on a y-alumina supportwhere the hydrogen pressure is 1.47×10⁷-1.96×10⁷ Pa and the temperatureranges from 250-330° C. Thermal hydrogenation is usually performed at160° C. to 320° C., at a pressure of 9.8×10⁵ to 11.7×10⁵ Pa and for aperiod typically of 1.5 to 4 hours. After hydrogenation, the reactormixture may be flashed and further separated to recover the resin. Steamdistillation may be used to eliminate oligomers, preferably withoutexceeding 325° C.

In a particularly preferred embodiment, the catalyst comprises nickeland/or cobalt on one or more of molybdenum, tungsten, alumina or silicasupports. In a preferred embodiment, the amount of nickel oxide and/orcobalt oxide on the support ranges from 2 to 10 wt %. The amount oftungsten or molybdenum oxide on the support after preparation rangesfrom 5 to 25 wt %. Preferably, the catalyst contains 4 to 7 wt % nickeloxide and 18 to 22 wt % tungsten oxide. This process and suitablecatalysts are described in greater detail in U.S. Pat. No. 5,820,749.

In another preferred embodiment, the hydrogenation may be carried outusing the process and catalysts described in U.S. Pat. No. 4,629,766. Inparticular, nickel-tungsten catalysts on γ-alumina are preferred.

While the pressure-sensitive adhesive formulations of the presentinvention exhibit excellent low temperature and ambient temperatureperformance as well as good die-cutting performance, they may alsoenhance elevated temperature performance. This may be accomplished bycross-linking techniques such as the use of electron beam (EB) radiationand ultraviolet (UV) radiation and chemical cross-linking. If employed,tackifying additives should be substantially saturated so that all ofthe energy of cure goes into cross-linking of the adhesives' elastomericcomponents.

The adhesive formulations may also contain additives well known in theart such as anti-block, anti-static, antioxidants, UV stabilisers,neutralisers, lubricants, surfactants, anti-nucleating agents and/orfillers. Preferred additives include silica, titanium dioxide,polydimethylsiloxane, talc, dyes, wax, calcium stearate, calciumcarbonate, carbon black, barium sulphate and magnesium silicate.

The adhesives of the invention may be used as pressure sensitiveadhesives, hot melt adhesives or contact adhesives and used inapplications such as tapes, labels, paper impregnation, hot-meltadhesives, including woodworking, packaging, bookbinding or disposables,sealants, rubber compounds, pipe wrapping, carpet backing, contactadhesives, road-marking or tire construction. They are particularlyuseful as hot-melt pressure sensitive adhesives used for labels wherethey impart improved die-cutting performance, and also improved adhesiveproperties, particularly improved shear performance.

In the Examples which follow, the block copolymers used in the adhesiveformulations were prepared by the process described in WO 95/14727 andthe desired ratio of radial and diblock copolymers was obtained byvarying the amount of coupling agent and/or by blending. The proceduresfor the preparation of the hot melt adhesive blends, and of the coatingsas well as the testing of the adhesive performances were as follow.

The hot melt pressure sensitive adhesives were prepared by mixing theblock copolymers with the tackifying resins in a laboratory z blademixer of 300 ml capacity, at a temperature of about 145° C. A smallamount of phenolic antioxidant was added to the blend to prevent itsdegradation during the blending process. The total mixing time was about70 minutes.

The tackifiers used were Escorez 1310 and ECR 373 from ExxonMobilChemical and Wingtack 10 from Goodyear.

Final blend viscosity was evaluated with a Brookfield viscosimeteraccording to a procedure based on ASTM D 3236-88.

The pressure sensitive adhesives were applied as a hot melt to asilicone coated paper at a coating weight of about 20 grams/sq meter,using an Acumeter laboratory coater with a slot die for extrusion of themolten adhesive at a temperature of 165° C. The lamination was doneaccording to industry practice, by transfer coating from the siliconecoater paper release substrate to a 80 g/sq meter vellum paper frontalsubstrate.

The adhesive performances were evaluated according to test methodspublished by FINAT, P.O. Box 85612 NL-2508 CH The Hague, for example,

-   -   FTM 1 for the peel adhesion at 180 degree    -   FTM 9 for the loop tack measurements    -   FTM 7 for the shear resistance

Migration was evaluated by comparing the whiteness of the paper frontalsubstrate after ageing at 60° C. and 70° C. for one and two weeks. Thewhiteness was evaluated with a Hunterlab spectrophotometer.

Dynamic rheological properties at 20° C. were determined on RDAII andSR-500 instruments manufactured by Rheometric Scientific, Piscataway,N.J. The former gives access to frequencies between 10⁻² to 100 rad.s⁻¹and temperatures lower than 20° C. (down to −70° C.) to reach the glassyregion obtained at higher frequencies. The SR-500 instrument, whichcovers a frequency range between 10⁻⁵ to 100 rad.s⁻¹ at room temperaturewas used for the terminal zone (lower frequencies). We used aplate-plate geometry for all experiments. The diameter of the platedecreases from 25 mm to 5 mm as temperature decreases in order tomaintain the actual rheometer torque between measurable limits.Frequency sweeps were carried out at deformation levels well within thelinear viscoelastic region. In order to broaden the range of accessibleexperimental frequencies, time-temperature superposition was appliedwith care. Measurements in the range of frequencies 10⁻⁵ to 10⁺² weremade at 20° C. To reach higher frequencies experiments at lowertemperature were performed and the measurements extrapolated to 20° C.

To ensure that experiments were conducted on bubble-free specimens,samples were degassed overnight under primary vacuum at about 90° C.Disks of adequate diameter were then compression molded, at atemperature systematically lower than the mixing temperature.

EXAMPLES

The following Examples A and B illustrate the Production of HighDiblock/Radial Block copolymer Mixtures via control of couplingefficiency.

Example A

To a 5 gallon stirred reactor under a nitrogen atmosphere were added12.5 kg of cyclohexane solvent and 84.0 g of a 0.17 M solution ofsec-butyl lithium in cyclohexane. The temperature of the reactor wasbrought to 75° C. and 339 g of styrene was added. Polymerization of thestyrene was allowed to continue for 36 minutes. The reaction mixture wascooled to 57° C. and 1692 g of isoprene was added. The isoprene wasallowed to polymerize for 46 minutes, during which the reactiontemperature reached a maximum of 92° C. At the end of the 46 minutes, 10grams of butadiene was added at 71° C. and it was allowed to polymerizefor an additional 34 minutes. Then 1.0 g of 0.87 M SiCl₄ in cyclohexanewas added all at once. The reaction was allowed to continue for another26 minutes before the reaction was terminated by addition of 3.0 ml ofisopropanol.

The resulting polymer was analyzed by GPC, and found to contain 82.0%diblock and 18.0% coupled radial block polymer. The radial blockcopolymer had 84% four arms, 16% three arms and no detectable two armsmaterial. The styrene content was 16.6 wt % and the molecular weight ofthe diblock was 78,150.

Example B

To a 5 gallon stirred reactor under a nitrogen atmosphere were added12.5 kg of cyclohexane solvent and 79.1 g of a 0.17 M solution ofsec-butyl lithium in cyclohexane. The temperature of the reactor wasbrought to 82° C. and 339 g of styrene was added. Polymerization of thestyrene was allowed to continue for 37 minutes. The reaction mixture wascooled to 58° C. and 1692 g of isoprene was added. The isoprene wasallowed to polymerize for 26 minutes, during which the reactiontemperature reached a maximum of 95° C. At the end of the 26 minutes, 10grams of butadiene was added at 71° C. and it was allowed to polymerizefor an additional 43 minutes. Then 3.1 g of 0.87 M SiCl₄ in cyclohexanewas added all at once. The reaction was allowed to continue for another31 minutes before the reaction was terminated by addition of 3.0 ml ofisopropanol.

The resulting polymer was analyzed by GPC, and found to contain 49.1%diblock, about 1% polystyrene homopolymer and the remainder coupledradial block polymer. The radial block copolymer had 78% four arms and15% three arms, with the remainder two arms material. The styrenecontent was 16.6 wt % and the molecular weight of the diblock was80,125.

The following additional Examples illustrate adhesive systems accordingto the present invention.

Styrene-isoprene four arms radial block copolymers having differentcontents of styrene-isoprene diblock copolymers and similar overallstyrene content were used in a hot melt formulation containing 31 wt %total of block copolymer, 27 wt % of Wingtack 10, and 42 wt % of Escorez1310 to which was added 0.4 wt % of Irganox 1076. The resulting hotmelts show the following characteristics: Comparative Example 1 Example2 Example 3 Example 4 Example 5 Radial polymer 268000 290800 328000332000 300000 molecular weight Diblock molecular 67000 72700 82000 8300075000 weight Styrene content (wt %) 20.5 17 18 17.8 17 Diblock content(wt %) 31 60 70 76 88 Brookfield Viscosity 6200 4960 5650 4460 1560(175° C.-mPa · s) 180° peel strength-N/25 mm Room temperature-glass 29cf 33.5 af 34.1 pt 36 29.5 cf 3° C.-glass 22 pt 18 pt 24 pt 22.6 pt Roomtemperature-PE 20.5 af 21 af 27 cf + pt 26 26 cf + pt 3° C.-PE 18.5 pt18.5 pt 25 pt 21 pt Loop Tack-N glass at room 23.5 af 22 af 28.3 af 3738 cf temperature glass at 3° C. 15 pt 6.5 af 15 pt 0.7 af 17 pt LoopTack-N Polyethylene at room 18 af 14 af 21.2 af 24 af 24 af temperaturePolyethylene at 3° C. 6.5 j 16.5 j + pt 5.0 j 18 pt Shear-roomtemperature- hours Steel-25 × 25 mm-1 kg >175 85-170 cf >150 cf 22-150cf 3 cf Migration-% reflection 1 week 60° C. 90 88.5 86.9 89.5 87 2weeks 60° C. 87 84 84.2 89 87.5 1 week 70° C. 82.5 85 83.8 82 80 2 weeks70° C. 80 77 80.6 68 79 Rheology Frequency where G′ = 1 10⁻¹ 1.7 10⁻¹1.1 10⁻¹ 1.7 10⁻¹ 3 10⁻¹ 1000 Pa (rad/s)* Tan delta at frequency 1.30.56 0.97 0.7 1.22 where G′ = 10,000 Pa*pt means paper tearcf means cohesive failureaf means adhesive failurej means jerking* when measured at 20° C.

FIG. 3 compares G′ of comparative Example 1, a standard hot meltpressure sensitive based on pure triblock copolymer and an acrylic basedadhesive.

The HMPSA adhesives of this invention have low viscosity, high shearproperties for radials up to 80% diblock content, associated withexcellent tack and peel performances at room and low temperature.

The dynamic rheological properties are shown in FIG. 4, where they arecompared with those of Comparative Example 1. As it can be seen, theplateau modulus at low frequencies is decreasing when the level ofdiblock in the radial copolymer is increasing. The systems of thepresent invention have much lower moduli than the product of comparativeExample 1.

G′ intersects a value of 10000 Pa at a frequencies higher than 10⁻³rad/s.

At such frequencies Tan delta varies preferably from 0.35 to 1.22,preferably 0.56 to 1.22, when measured at 20° C.

The die-cutting performance of the adhesive of Example 4 was tested on aprinting die-cutting machine, and was compared with a commercial HotMelt Pressure Sensitive formulation based on linear block copolymershaving an overall diblock content of 75% and with an acrylic basedadhesive. The tests were performed using different types of die shapes.The results are shown in FIG. 5.

The results shown in FIG. 5, demonstrate that the reduced elasticbehavior as shown in FIG. 4 (lower plateau modulus, higher loss factorTan delta) provide to hot melt pressure sensitive adhesives based onradial copolymer with high diblock content significantly betterdie-cutting performance than commercially available copolymer basedadhesive formulations and is close to the die-cutting behaviour ofacrylic based adhesives.

We have also found that the radial block copolymer mixtures of thepresent invention have lower tensile strength and are softer and moretacky than the previous mixtures with a lower diblock content. Thisrenders the polymers useful in applications such as sound deadening,shock absorption and polymer modification.

1. A mixture of radial styrenic block copolymer and styrenic diblockcopolymer comprising from 60 wt % to 10 wt % of radial styrenic blockcopolymer and from 40 wt % to 90 wt % of a styrene diene diblockcopolymer wherein the styrene diene diblock copolymer is a styreneisoprene diblock copolymer and/or a styrene butadiene diblock copolymerand wherein when the diblock copolymer is a styrene butadiene diblockcopolymer it has a styrene content of 10 wt % to 30 wt %.
 2. A mixtureaccording to claim 1 in which, in the case the radial styrenic blockcopolymer is a styrene isoprene block copolymer, it comprises i) apolystyrene block segment and ii) a polyisoprene block segment having anend which comprises butadiene, wherein the block copolymer ischaracterized by the formula:(pS−pl−pB)_(n)X pS being polystyrene, pl being polyisoprene, pB beingpolybutadiene, X being the residue of a multifunctional coupling agentused in the production of the radial block copolymer and n being anumber greater than or equal to 3 and representing the average number ofbranches appended to X, and further wherein the pS component is presentin an amount of at least 10 parts to 30 parts per 100 parts by weight ofthe radial block copolymer; wherein the weight amount of polybutadienein the pI−pB segment is less or equal to 10 wt %.
 3. Cancelled
 4. Amixture according to claim 2 wherein the weight amount of polybutadienein the pl−pB segment is less than or equal to 5 %.
 5. A mixtureaccording to any of claims 1, 2 or 4 wherein the average numbermolecular weight of the polystyrene component is between 10,000 and15,000.
 6. A mixture according to any of claims 2 or 4 wherein n ispredominately
 4. 7. A mixture according to claims 1, 2 or 4 in which theradial block copolymer has a molecular weight (Mw) from 200,000 to500,000 g/mole.
 8. A mixture according to claims 1, 2 or 4 in which thepure radial copolymer has an overall styrene content from 10 wt % to 30wt %.
 9. A mixture according to claims 1, 2 or 4 in which the styrenicradial copolymer has a molecular weight from 240,000 to 400,000 g/mole.10. Cancelled
 11. A mixture according to claims 1, 2 or 4 in which thediblock copolymer contains from 10 to 30 wt % styrene.
 12. A mixtureaccording to claims 1, 2 or 4 in which the styrene diene diblockcopolymer is a styrene-butadiene diblock copolymer and has a molecularweight of from 50,000 to 150,000 g/mole.
 13. An adhesive comprising atackifier and a mixture of a radial styrenic block copolymer and astyrene diene diblock copolymer comprising from 60 wt % to 10 wt % ofthe radial styrenic block copolymer and from 40 wt % to 90 wt % of thestyrenic diene diblock copolymer wherein the styrene diene diblockcopolymer is a styrene isoprene diblock copolymer and/or a styrenebutadiene diblock copolymer; wherein when the diblock copolymer is astyrene butadiene diblock copolymer it has a styrene content of 10 to 30wt %.
 14. An adhesive according to claim 51 in which the radial blockcopolymer comprises a four arms radial copolymer.
 15. An adhesiveaccording to any of claims 13, 51 or 14 in which the radial blockcopolymer has a molecular weight (Mw) from 200,000 to 500,000 g/mole.16. An adhesive according to any of claims 13, 51 or 14 in which thepure radial copolymer has an overall styrene content from 10 wt % to 30wt %.
 17. Cancelled
 18. An adhesive according to claims 13, 51 or 14, inwhich the diblock copolymer contains from 10 to 30 wt % styrene.
 19. Anadhesive according to any of claims 13, 51 or 14 in which the styrenicradial copolymer has a molecular weight from 240,000 to 400,000 g/mole.20. Cancelled
 21. An adhesive according to any of claims 13, 51 or 14,in which the tackifier is a hydrocarbon resin.
 22. An adhesive accordingto claim 21 in which the tackifier is an aliphatic C₅ resin.
 23. Anadhesive according to claim 21 in which the tackifier is an aromaticresin.
 24. An adhesive according to claim 21 in which the tackifier isan aromatic/aliphatic C₅/C₉ resin.
 25. An adhesive according to any ofclaims 22 to 24 in which the resin is hydrogenated.
 26. An adhesiveaccording to any of claims 13, 51 or 14 in which the tackifier is arosin, rosin ester or a polyterpene resin.
 27. An adhesive according toclaim 26 in which the tackifier is hydrogenated.
 28. An adhesiveaccording to any of claims 13, 51 or 14 having a storage modulus plateauat low frequencies below 8,000 Pa, when measured at 20° C.
 29. Anadhesive according to any of claims 13, 51 or 14 in which G′ intersectsa value of 10,000 Pa at a frequency higher than 0.001 rad/s, whenmeasured at 20° C.
 30. An adhesive according to any of claims 13, 51 or14 having a loss factor Tan delta between 0.2 and 1.3 at the frequencyat which the storage modulus intersects a value of 10000 Pa, whenmeasured at 20° C.
 31. An adhesive according to any of claims 13, 51 or14 further containing a plasticizing oil.
 32. An adhesive according toclaim 31 containing from 5 to 20 wt % of the plasticizing oil.
 33. A hotmelt pressure sensitive adhesive which is an adhesive according to anyof claims 13, 51 or
 14. 34. A process for the production of labelscomprising, applying as a hot melt an adhesive, according to any of theclaims 13, 51 or 14 said adhesive being applied to a release liner, andsubsequently laminating the coated release liner to a face stock, andconverting the laminate into a label stock.
 35. The use in an adhesiveof a mixture of a radial styrenic block copolymer and a styrene dienediblock copolymer comprising from 60 wt % to 10 wt % of the radial blockcopolymer and from 40 wt % to 90 wt % of the styrene diene diblockcopolymer wherein the styrene diene diblock copolymer is a styreneisoprene diblock copolymer and/or a styrene butadiene diblock copolymer;wherein when the diblock copolymer is a styrene butadiene diblockcopolymer it has a styrene content of 10 wt % to 30 wt %.
 36. The useaccording to claim 52 in which the radial block copolymer comprises afour arms radial styrenic copolymer.
 37. The use according to any ofclaims 35, 52 or 36 in which the radial block copolymer has a molecularweight (Mw) from 200,000 g/mole to 500,000 g/mole.
 38. The use accordingto any of claims 35, 52 or 36 in which the radial copolymer has anoverall styrenic content from 10 wt % to 30 wt %.
 39. Cancelled
 40. Theuse according to any of claims 35, 52 or 36 in which the diblockcopolymer contains from 10 to 30 wt % styrene.
 41. The use according toany of claims 35, 52 or 36 in which the styrenic radial copolymer has amolecular weight from 240,000 to 400,000 g/mole.
 42. Cancelled
 43. Theuse according to any of claims 35, 52 or 36 together with a tackifier.44. The use according to claim 43 in which the tackifier is ahydrocarbon resin.
 45. The use according to claim 44 in which thetackifier is an aliphatic C₅ resin.
 46. The use according to claim 44 inwhich the tackifier is an aromatic resin.
 47. The use according to claim44 in which the tackifier is an aromatic/aliphatic C₅/C₉ resin.
 48. Theuse according to any of claims 44 to 47 in which the resin ishydrogenated.
 49. The use according to claim 43 in which the tackifieris a rosin, rosin ester or polyterpene resin.
 50. The use according toclaim 49 in which the tackifier is hydrogenated.
 51. An adhesiveaccording to claim 13 in which, in the case the radial styrenic blockcopolymer is a styrene isoprene block copolymer, it comprises i) apolystyrene block segment and ii) a polyisoprene block segment having anend which comprises butadiene, wherein the block copolymer ischaracterized by the formula:(pS−pl−pB)_(n)X pS being polystyrene, pl being polyisoprene, pB beingpolybutadiene, X being the residue of a multifunctional coupling agentused in the production of the radial block copolymer and n being anumber greater than or equal to 3 and representing the average number ofbranches appended to X, and further wherein the pS component is presentin an amount of at least 10 parts to 30 parts per 100 parts by weight ofthe radial block copolymer; wherein the weight amount of polybutadienein the pI−pB segment is less or equal to 10 wt %.
 52. The use accordingto claim 35 in which, in the case the radial styrenic block copolymer isa styrene isoprene block copolymer, it comprises i) a polystyrene blocksegment and ii) a polyisoprene block segment having an end whichcomprises butadiene, wherein the block copolymer is characterized by theformula:(pS−pl−pB)_(n)X pS being polystyrene, pl being polyisoprene, pB beingpolybutadiene, X being the residue of a multifunctional coupling agentused in the production of the radial block copolymer and n being anumber greater than or equal to 3 and representing the average number ofbranches appended to X, and further wherein the pS component is presentin an amount of at least 10 parts to 30 parts per 100 parts by weight ofthe radial block copolymer; wherein the weight amount of polybutadienein the pI−pB segment is less or equal to 10 wt %.